Nitroazoline compounds and process therefor



United States Patent 3,354,171 NHTRQAZDLHNE COMPGUNDS AND PRUCESS THEREFOR Herbert L. Wehrmeister, Terre Haute, Ind., assignor to Commercial Solvents Corporation, New York, N.Y., a

corporation of Maryland No Drawing. Filed Sept. 20, 1965, Ser. No. 488,776 23 Claims. (Cl. 260307) This invention generally relates to new nitroazoline compounds. In a first aspect, it relates to new nitrooxazoline and nitroimidazoline compositions and process for the production thereof. In a second aspect it relates to 2-(nitroalkyD-Z-azolines including aryl-, alkyl-, and alkenylsubstituted nitroalkyl azolines. In a more particular aspect it relates to the nitroazoline compounds 2- 3-nitro-3 -alkyl) -2-oxazolines,

2-( 1-alkyl-3 -nitroalkyl) -2-oxazolines,

2- l-arylalkyl-3 -nitroalkyl) -2-oxazolines, 2-(1-alkenyl-3-nitroalkyl)-2-oxazolines,

2-( 1-aryl-3 -nitroalkyl) -2-oxazolines,

2- 3-nitro-3-alkyl -2-imidazolines,

2-( 1-alkyl-3 -nitroalkyl -2-imidazolines,

2-( l-arylalkyl-3 -nitroalky1) -2-irnidazolines, 2- 1-alkeny1-3-nitroalkyl -2-imidazolines, 2-(1-aryl-3-nitroalkyl)-2-irnidazolines,

and a process for the production thereof.

2-oxazolines and Z-imidazolines have the following general formula:

where X is either the oxygen of the oxazoline ring, or it is the imide nitrogen of the imidazoline ring. It is conventional nomenclature to assign to X the position 1 and to number the remaining constituents of the ring in numerical sequence in a direction which will give the N the lowest number, i.e. in a counter-clockwise direction in the above formula. Thus the carbon atom between X and N is position 2, N is 3, etc. A carbon atom attached to the carbon atom in the 2-position is referred to in this specification as the alpha carbon atom.

There are numerous references in the art to the preparation of substituted oxazolines and imidazolines and compounds having substitution on each position of the ring are known. Several methods of preparing oxazolines and imidazolines are known but the most common method is to react an organic monocarboxylic acid with a 1,2- alkanolamine followed by dehydration to produce an oxazoline, or to react the organic acid with a 1,2-diamine followed by dehydration to produce the imidazoline. The carboxylic acid residue forms the substituent in the-2-position, and other substituents, if any, have usually been provided by the structures of the alkanolamines and diamines respectively.

There has been no disclosure in the prior art of either oxazolines or imidazolines of a method of substituting a nitroalkyl group on the alpha carbon atom after the ring has been formed. Neither has there been a disclosure of a nitroaliphatic radical attached to the alpha carbon atom in the 2-position.

It is an object of this invention to provide new nitroazoline compounds and a method for the preparation thereof.

nitro-3 -alky1) -2-oxazolines.

A third object of this invention is to provide 2-(1-alkyl- 3-nitroalkyl)-2-oxazolines.

A fourth object of this invention is to provide 2-(1- ary1alkyl-3 -nitroalkyl) -2-oxazolines.

A fifth object of this invention is to provide 2-(1- alkenyl-3-nitroalkyl -2-oxazo1ines.

A sixth object of this invention is to provide 2-(laryl-3-nitroalkyl -2-oxazolines.

A seventh object of this invention is to provide 2-(3- nitro-3 -alkyl) -2-imidazolines.

Another object of this invention is to provide 2-(1- alkyl-3 -nitroalkyl -2-imidazolines.

A further object of this invention is to provide 2-(1- arylalkyl-3 -nitroalkyl -2-imidazolines.

A still further object of this invention is to provide 2-( 1-alkenyl-3-nitroalkyl)-2-imidazolines.

Still yet another object of this invention is to provide 2- 1-aryl-3-nitroalkyl)-2-imidazo1ines.

Other objects of this invention will be readily apparent to those skilled in the art.

The azoline compounds .2- 3-nitro-3-alkyl -2-oxazolines,

are embraced by this invention. These oxazolines and imidazolines are represented by the following general where Y can be an alkyl radical, aryl radical, arylalkyl, or hydroxyalkyl radical; R is hydrogen, alkyl, alkenyl, aryl or arylalkyl radical of from 1 to about 20 carbon atoms; R and R, can be hydrogen, alkyl radicals having from 1 to 3 carbon atoms, hydroxymethyl or the group acyloxy methyl, with the proviso that when X is R and R, can be hydrogen or alkyl radicals of from 1 to 3 carbon atoms. R and R can be the same or they can be different.

When X is -O-, the following oxazoline is obtained:

When R is hydrogen, the following oxazoline is obtained:

I YN- the following imidazoline is obtained:

. a HzC|1-CR2 Y-N N (1 01-1 H(i]CHz-C-CH3 R1 N02 and when R is hydrogen, the following imidazoline is obtained:

l a H2C CRz Y-N N F E HzCCH2-CCH The new compositions of this invention can be prepared by reacting about 1 mole of a secondary nitroalkane in the presence of a condensationcatalyst with about 1 mole of a Z-ethenyl azoline having the general formula:

a t-t R1(|J=CH2 where X, R R and R have been previously defined. When X is O- and R is hydrogen, the compound prepared is a 2-(3-nitro 3-alkyl)-2-oxazoline. When X is O-- and R is alkyl, the compound prepared is a 2-(1- alkyl-3-nitroalkyl)-2-oxazoline. When X is O- and R is arylalkyl the compound prepared is a 2-(1-arylalkyl-3-- nitroalkyl)-2-oxazoline. When X is O- and R is alkenyl, the compound prepared is a 2-(1-alkenyl-3-nitroalkyl)-2-oxazoline. When X is O and R is aryl, the compound prepared is a 2-(l-aryl-3-nitroalkyl)-2-oxazoline. When X is and R is arylalkyl, the compound prepared is a 2-(1-ary1- alkyl-3-nitroalkyl)-2-imidazoline. When X is and R is alkenyl, the compound prepared is a 2-(1- alkenyl-S-nitroalkyl)-2-imidazoline. When X is and R is aryl, the compound prepared is a 2-(l-aryl-3- nitroalkyl -2-imid azoline.

In general the reaction is conducted by charging the reactants and catalyst into a suitable reaction vessel equipped with a reflux condenser and an agitator. A solvent can be used if desired and generally a solvent is preferred. The amount of catalyst used is preferably from about 0.5% to about 5% by weight based on the weight of the azoline, i.e. the oxazoline or imidazoline. Heat is applied from a heat source and the mixture is reacted at reflux temperature until the nitroalkane is consumed. When nitroalkane is no longer condensing at the top of the reflux column, and the pot temperature has risen to at least C., the reaction is substantially complete. The entire product of the reaction can be used if desired, but usually it is preferred to purify it. Any known method of purification, such as extraction or distillation can be used.

Distillation is a preferred method for compounds having suflicient thermal stability. To produce a distilled crude, the reaction product is distilled at a reduced pressure of from about 10 to about 15 mm., and the heads and tails are discarded. If still further refinement is preferred, the distilled crude is fractionated at a pressure of from about 1 to about 5 mm. The temperature at which these distillations occur will usually be less than 200 C. and will vary according to the ethenyl azoline used as the starting material as Well as the pressure at which the distillation is conducted. In general, if R is a long chain radical, the temperature tends to be higher than if R is a short chain radical.

The preparation of a compound by this reaction is described in Example 3.

In another embodiment of this invention the ethenyl azoline is prepared in situ and is then reacted with the nitroalkane to form the nitro derivative. One method is to react about 1 mole of a 2-substituted azoline, e.g. a 2- alkyl azoline, a 2-alkenyl azoline, or a Z-arylalkyl azoline with about 1 mole of a 1-hydroxy-2-alkyl-2-nitroalkane, e.g. 2-nitro-2-methyl-l-propanol, preferably in the presence of a condensation catalyst. This reaction releases about 1 mole of water, which must be removed from the reaction mixture before the reaction is complete. The reaction is conveniently conducted in the presence of a water-entraining solvent at reflux temperatures and at arnbient pressures. The heating is continued until water of reaction is no longer being released as can be determined by use of a water separator at the top of the reflux column. The water-entraining solvent, such as hexane, octane, benzene, toluene, xylene, 2-nitropropane, etc., reduces the viscosity of the reaction mixture and removes azeotropically the Water of reaction. After removal of water and water-entraining solvent by distillation, the entire product of the reaction can be used if desired but usually it is preferred to purify it.

It is known that hydroxynitroalkanes revert to nitroalkane and aldehyde under alkaline conditions, so in this embodiment, it is possible that the hydroxynitroalkane does decompose under the reaction conditions to yield formaldehyde and nitroalkane; the formaldehyde then reacts with the 2-substituted azoline to yield the ethenyl azoline which, in turn, reacts as previously described with the nitroalkane residue released by the hydroxynitroalkane. The preparation of a compound of this invention by this embodiment is described in Example 1.

The preferred embodiment of this invention is to prepare the ethenyl azoline in situ by condensing a Z-su-bstituted azoline with formaldehyde from a formaldehyde source and reacting the resulting product with a secondary nitroalkane, preferably in the presence of a condensation catalyst. This embodiment is preferred to the two described previously because of the lower costs of the reactants. The reaction releases 1 mole of Water and in general is conducted in the same manner as the one just described. The nitroalkane can be introduced to the reaction vessel at the start of the reaction as in Example 2, or it can be added later after the reaction of formaldehyde with the azoline is complete as in Example 14.

Further details on the preparation of the compounds of this invention are given in the examples. Henceforth these nitro-azolines will be referred to as nitro-oxazolines and nitro-imidazolines.

The nitro-oxazolines and nitro-imidazolines of this invention are useful as plasticizers for nitrocellulose and as intermediates for the preparation of amino-oxaz-olines and amino-imidazolines.

The nitro-oxazolines and nitro-imidazolines of this invention are employed as plasticizers in nitrocellulose lacquers in the same manner as is used for other such plasticizers as is known to those skilled in the art. In general, these nitro-oxazolines and nitro-imidazolines are employed in conventional lacquers in an amount of [from about 75% to about 125% by weight of the weight of the nitrocellulose.

Amino-oxazolines and amino-irnidazolines can be prepared from the nitro-oxazolines and nitro-imidazolines of this invention by hydrogenation in the presence of a hydrogenation catalyst, e.g. Raney nickel at about 1000 p.s.i.g. at about 30 C. in accordance with procedures known in the art. However, if R R or R contain unsaturated linkages, they will probably be hydrogenated in the presence of Raney nickel.

Azolines useful for the preparation of the nit-nooxazolines and nitro-imidazolines in the practice of this invention can be obtained commercially or they can be prepared. Commercially available 2-substituted oxazolines and 2-substituted imidazolines having an alkyl, arylal'kyl or alkenyl radical in the 2-position are satisfactory for the practice of this invention. Several methods of preparation of 2-substit-uted oxazolines and 2-substituted imidazolines are known in the art, and any method giving an alkyl, alkenyl, or arylalkyl radical in the 2-position will give oxazolines and imidazolines satisfactory for the practice of this invention. Oxazolines substituted in the 4- and 5-positions and imidazolines substituted in the 1-, 4-, and 5-positions are also satisfactory provided they have an alkyl, alkenyl, or arylalkyl radical on the 2-position. One procedure which has given satisfactory results for preparing such compounds is given by H. L. Wehrmeister, J. Org. Chem. 26, 3821 (1961).

The ethenyl azolines employed in the practice of this invention are readily prepared from 2-alkyl oxazolines, 2-arylalkyl oxazolines, 2-alkenyl oxazolines, 2-alkyl imidazolines, '2-arylalkyl imidazolines, and 2-alkenyl imidazolines by treating them with a formaldehyde source such as formaldehyde or paraformaldehyde as is known by those skilled in the art and as described in Example 14. Also, a satisfactory procedure is given by H. L. Wehrmeister, J. Org. Chem. 27, 4418 (1962).

In general, Z-substituted oxazolines can be readily prepared by reacting an aliphatic or aromatic monocarboxylic acid having 2 or more carbon atoms with an alkanolamine having the following general structure:

where R and R are alkyl radicals of from 1 to 3 carbon atoms or hydroxymethyl. R and R can be the same or they can be different. These alkanolamines include but are not limited to 2-amino-2-methyl-l-propanol; 2-amino- 2 methyl-1,3-propanediol; Z-amino-Z-ethyl-1,3-propanediol; Z-amino-2-hydroxymethyl-1,3-propanediol. When either R or R or both, are hydroxyalkyl, the resulting hydroxyoxazoline can be esterified with aliphatic or aromatic monocarboxylic acids according to methods known in the art and these oxazoline esters are also useful in the practice of this invention. When the carboxylic acid is saturated, R is alkyl; when the carboxylic acid is unsaturated R, is alkenyl; when the carboxylic acid is a member of the phenyl aliphatic acid series, R is arylalkyl or aryl, i.e. if the monocarboxylic acid is phenyl acetic acid, R is aryl.

When the alkanolamine is a triol, both R and R will be hydroxymethyl if 1 mole of a monocarboxylic acid is used to form the oxazoline. These hydroxymethyl groups can then he esterified by an aliphatic, an aromatic or an aryl alkyl monocarboxylic acid to form acyloxymethyl groups. Either the same acid used to form the oxazoline can be employed, or a different one can be used. When it is preferred that the hydroxymethyl group be esterified with the same acid used to form the oxazoline, it is convenient to react the alkanolamine with 3 moles of acid whereupon the di-ester oxazoline is formed in a single step.

Similarly, if the alkanolamine is a diol, and 1 mole of acid is used, either R or R is hydroxymethyl and the other is an alkyl group of from 1 to 3 carbon atoms. The hydroxymethyl group can similarly be esterified, either at the time of oxazoline formation by the use of 2 moles of acid, or in a separate step.

Similarly, 2-alkyl or 2-alkenyl imidazolines can be readily prepared from a monocarboxylic acid having 2 or more carbon atoms by reacting it with a diamine having the following general formula:

where R and R are hydrogen or alkyl radicals of from 1 to 3 carbon atoms. R and R can be the same or they can be different. Y is lower alkyl, aryl, arylalkyl or hydroxyalkyl. These diamines include but are not limited to N -isopr0pyl-2-methyl-l,2-propanediamine; N -phenyl- 2 methyl 1,2-propanediamine; N -(2-hydroxyethyl)-2- methyl 1,2-propanediamine; N-(2-aminoisobutyl)butylamine; and N-(2-aminoisobutyl)benzylamine.

The monocar'boxylic acids which can be used to form the oxazolines, imidazolines and their esters can be represented by the formula R CH COOH where R can be hydrogen, alkyl, arylalkyl, alkenyl or aryl radical of from 1 to about 20 carbon atoms. These acids are the saturated and unsaturated acids of the fatty acid series, including phenyl substituted fatty acids, beginning with acetic acid. There is no known upper limit to the length of the carbon chain which can be employed, but it is practical to utilize the acids having 22 carbon atoms or less because of their relatively low cost. Examples of such acids include but are not limited to acetic, phenylacetic propionic, phenylpropionic caproic, coconut oil fatty acids, tall oil fatty acids, oleic acid, stearic acid, fish oil acids, and the like. Also mixtures of these acids can be employed in preparing these oxazolines and imidazolines.

The nitroalkanes used in the practice of this invention are secondary nitroalkanes having from 3 to 6 carbon atoms in the molecule, including but not limited to 2- nit-ropropane, 2-nitrobutane, nitrocyclohexane, and preferably 2-nitropropane. The monohydroxy nitroalkanes used in the practice of this invention'are those having from 4 to 6 carbon atoms in the molecule and having the nitro group and an alkyl group in the 2-position, preferably 2-nitro-2-methyl-l-propanol. The commercial grade materials are fully satisfactory for the practice of 1 this invention.

The products of this invention and process for the preparation therefor can best be illustrated by the following examples:

Example 1 The preparation of 2-(3-nitro-1,3-dimethylbutyl)-4,4- dimethyl-2-oxazoline was conducted as follows:

Into a 500 ml. round bottomed flask was charged 60 g. (0.5 mole) of 2-nitro-2-methyl-l-propanol, 74.0 g. (0.58 mole) of 2-ethyl-4,4-dimethyl-2-oxazoline, and 1 gram of iodine catalysts. The nitromethylpropanol dissolved readily in the oxazoline with adsorption of heat. Toluene, (100 ml.) was added to assist in removal of water of reaction. The flask was connected .to an 18" Vigreux column equipped with a water separator and a reflux condenser and sufficient heat was applied to initiate reflux. Heating at reflux was continued for about 17 hours during which time the temperature gradually rose to about 164 C.

- The residue was flash distilled. One fraction was taken at B.P. 39-156 C. at 20 mm., and a second one boiling at 88-172 C. at 1 mm. The residue was discarded, the two fractions combined and redistilled through an 18" Vigreux column. The product recovered was predominantly 2 (3 nitro 1,3 dimethylbutyl) 4,4 dimethyl- 2-oxazoline and analyzed as follows:

The quantity of catalyst chosen for this example Was greater than that in Example 1 to reduce the reaction period. The 2-nitropropane acted as the water-entraining solvent until it was substantially consumed by reaction. The flask was equipped with a sealed stirrer and thermometer and was attached to an 18" Vigreux column equipped with a water separator and a reflux condenser. The mixture was heated at reflux for about 9 hours during which time the temperature rose to about 152 C.

The pot residue was flash distilled and a cut boiling 10 at 106 C. to 125 C. at 1.5-2.5 mm. was fractionated through an 18" Vigreux column. A relatively pure cut boiling at 90-110 C. at 1.5 mm. was taken as the principal product.

Example 3 Example 2 is repeated except that 2-isopropenyl-4,4-dimethyl-Z-oxazoline is used in place of 2-ethyl-4,4- dirnethyl 2- oxazoline and the paraformaldehyde is omitted. The expected product, 2-(3-nitro-1,3-dimethylbutyl)-4,4-dimethyl-2-oxazoline, is obtained.

Examples 421 the substituents as identified in Table 1 in the R R and R positions, when the starting oxazolines are prepared from the acids and alkanolamines listed in Table 1.

TABLE 1 Ratio Starting Oxazoline prepared from Identity of- Ex. Aoid/ N0. Hydroxy Group Acid Alkanolamine R R R 2-amin0-2-n1ethyl-1-propan0l H CH CH3 2-amino-2-methyl-L3-propancdiol. H CH CH OH TrisQiydroxyrnethyD- H CHZOH CHzOII aminomethane. d 0 H CHzOOCCIIz CHzOOCCHa 1-am1no-2-methyl-1,3-propanedioL H CHzOOCCH; CH 2-amin0-2-ethyl-l,3-propanedi0l H CHzOOCCHa C2Hs y d H CHQOH 0 1a 11 1:2 Propiqmc .d0 CH3 C1115 CHQOH 12 1:1 Caproie Tris(hydroxymethyl)- CAHQ CHzOOCOsHu CHzOOCC H aminomethane. 2-ami no-2-methyl-l,3propanedi0l C Hzl CH3 CHzOH Z-amrno-Z-ethyl-l,3-propanediql C1011 C2115 CH2OOCC11Hz3 2-arnmo-2-methyl-1,3-propaneoio1- C H CH; CHzOH Trmp g y t ynamino- 010E113 C iOOCCl'IHHG orrioooonHa me H 11 1:3 Behemic CHzOH omorr 18 1:1 01610. d0 CHaOOCCnHaa CHzOOCCnI-Ias 19-.-" 1:1 Linoleie Q-amino-l-butano C 11 H 20 1:1 Phenylacetid. Tris(hydr0xymethyl)amino- C H CH O O C CH (311 0 O O CH;

methane.

lfi fi fl CHi00o(oH2)2 orrlooo onz z propionie.

Molecular weight (calc.) 228.3 Example 22 N e livalen 23 .6 sgg p it t g 0 2 (3 nitro-3-methylbutyl)-4,4-b1s(benzoxymethyl)- 2-oxazoline is prepared according to the procedure of E Nitrogen (theo. 12.3%), percent 11.8

ample 2 except that 2-methyl-4,4-b1s(benzoxymethyl)-2- Infrared adSOTPHO oxazoline 360 is used in lace of Z-eth 1-4 4 dimeth 1 Spectrum Cons1stent with subject structure. P y y o 2-oxazol1ne. Boiling range at 1 mm, C. 87-93 2 (3 nitro 1,3 dimethylbutyl) 4,4 dimethly- 2-oxazoline was prepared with 2-nit-ropropane and paraformaldehyde in place of the 2-nitro-2-methyl-1-propanol used in Example 1. To a 500 ml. flask was charged paraformaldehyde 33 g., 2-e-thyl-4,4-dimethyl-2-oxazoline 131.5 g., 2-nitropropane 153.5 g., and iodine catalyst 4 g.

Example 23 The preparation of 2-(3-nitro3-methyl)-4,4-dimethyl- 2-oxazoline Was conducted as follows:

Into a 500 ml. flask was charged paraformaldehyde 33 g. and 2,4,4-trimethyl-2-oxazoline 115 g. This mixture was heated with stirring for 2 hours at -84 C., and then 150 g. of 2-nitropropane and 5 g. sodium bisulfate were added. This mixture was then heated at reflux temperature for 4 hours during which time the temperature rose to 137 C.

The pot residue was flash distilled through an 18" Vigreux column and a cut boiling at 93-113 C. at 0.8 mm. was taken. This cut was fractionated through an 18" Vigreux column and a cut was taken at -94 C. and

Q 0.3 mm. yielding 54 g. of product. Analytical data confirmed the expected structure.

Example 24 The preparation of 2 (3-nitro-l,3-dimethylbutyl)-1- isopropyl 4,4 dimethyl-Z-imidazoline was conducted as follows:

To a 500 ml. flask was charged 1-isopropyl-2-ethyl-4,4- dimethyl-Z-imidazoline 85 g., paraformaldehyde 16.5 g., 2-nitropropane 45 g., benzene 50 ml., zinc chloride catalyst 2 g. The mixture was heated at reflux with stirring at reflux temperature (132136 C.) for about 5 hours. The

mixture was then flash distilled. The heads and tails were discarded and the remainder was fractionated through radicals of from 1 to 7 carbon atoms; R is selected from Yl I- R and R are selected from hydrogen and alkyl radicals of from 1 to 3 carbon atoms.

2. The nitro-oxazoline compounds represented by the an 18 Vigreux column. A relatively pure cut was made followin Structural form ula. at MM? 0. and at 0.3 mm. g

The nitro-imidazoline produced in the above reaction is incorporated in a nitrocellulose lacquer as the plasticizer H2C-CR2 therefor in an amount about equal to the weight of the 0 1; nitrocellulose. A durable, flexible film is formed when 20 CH the lacquer is applied to the surface of an object and al- I lowed to dry. H-CIICHTCCH3 Example R1 N02 The experiment of Example 24 is repeated except that wherein R is selected from the group consisting of hydro- 2-nitro-2-methyl-l-propanol is used in place of para- 25 gen and alkyl, arylalkyl, :alkenyl, and aryl radicals havformaldehyde and 2-nitropropane. 2-(3-nitro-1,3-dimethyling from 1 to about 20 carbons atoms; and R and R are butyl)-1-isopropyl-4,4-dimethyl-2-imidazoline is obtained. selected from thegroup consisting of hydrogen, alkyl radicals having from 1 to 3 carbon atoms, hydroxymethyl Example 26 radical, and the acyloxymethyl group, said acyl group expeflmeflt of Example 1S p f pl thlt 30 being an aliphatic, aromatic or aralkyl monocarboxylic 1 p py P P Y l y 1S acyl group of from 2 to 22 carbon atoms. employed i the Stamng azohne Place of l'lsopropyl'z 3. The nitro-oxazoline compounds represented by the ethyl-4,4-d1methyl-2-1midazoline and the paraformaldefollowing formula: hyde is omitted. 2 (3 nitro-l,3-dimethylbutyl)-1-isor R I propyl-4,4-dimethyl-2-imidazo1ine is obtained. C C- Examples 27-39 H2 1 R2 0 N Following the procedure of Example 24, compounds corresponding to the general formula are obtained having EH the following substituents in the R R and R and Y 40 2 2 a positions. N02

TABLE 2 Starting Imidazoline prepared from Identity of Exlalmple Acid Diamine R1 R2 R; Y

N -isopropyl-2-methy1-1,2-propanediamine. CH3 CH3 C3H1 N phenyl-2-methyl-l,2-propanediamine CioHn CH3 CH3 C8115 N -(Z-hydroxyethyl)-2-methy1-1,2-propanediamine--. CwHss CH3 CH3 C2H4OH N-(2-aminoisobutyl)butylamine CmHn CH3 CH3 C4H9 N-(2-aminoisobutyl)benzylamine CH3 CH3 06H5CH1 N -(Z-hydroxyethyl)-2-methyl-1,2-pro nediami H CH3 CH3 CzHrOH l,2-ethylene diamine H H N -phenyl-2-methyl-1,2-propane am CH3 CH3 C5115 H- CH3 CH3 CBHE N -benzyl-2-rnethyll,Z-propanediamine- H CH3 CH3 C H CH N -ethyl2-methyl-l,2-propanediamine H CH3 CH3 2H5 d N -hydroxyethyl-2-methyl-1,2-propanediamine H CH3 CH3 CgHrOH Pheny1pr0pi0uic N -isopropy1-2-methyl-1,2-propanediamine CuHsCHz CH3 CH3 3H7 What is claimed is:

wherein R and R are selected from the group consist- 1. The nitro-azoline compounds represented by the ing of hydrogen, alkyl radicals having from 1 to 3 carbon following structural formula:

a I-IzC-( -R2 HC-CHzCCHa I'M NO:

wherein X is selected from the group consisting of --O-- and wherein Y is selected from the group consisting of hydrogen and lower alkyl, aryl, arylialkyl and hydroxyalkyl atoms, hydroxymethyl radical, and the acyloxymethyl group, said acyl group being an aliphatic, aromatic or aralkyl monocarboxylic acyl group of from 2 to 22 carbon atoms.

4. 2-(3-nitro-3-methylbutyl) 4,4 dimethyl-Z-oxazoline.

5. The nitro-oxazoline compounds represented by the following structural formula:

wherein R is an alkyl radical having from 1 to carbon atoms and R and R are selected from the group consisting of hydrogen, alkyl radicals having from 1 to 3 carbon atoms, hydroxymethyl radical, and the acyloxymethyl group, said acyl group being an aliphatic, aromatic or aralkyl monocar-boxylic acyl group of from 2 to 22 carbon atoms.

6. The nitro-oxazoline compounds represented by the following structural formula:

wherein R is an aryl alkyl radical corresponding to the formula where x is an integer of from 1 to 14 and R and R are selected from the group consisting of hydrogen, alkyl radicals having from 1 to 3 carbon atoms, hydroxy methyl radicals and the acyloxymethyl group, said acyl group being an aliphatic, laromatic or aralkyl monocarboxylic acyl group having from 2 to 22 carbon atoms.

7. The nitro-oxazoline compounds represented by the following structural formula:

wherein R is an .alkenyl radical having from 2 to 20 carbon atoms and R and R are selected from the group consisting of hydrogen, alkyl radicals having from 1 to 3 carbon atoms, hydroxymethyl radical, and the acyloxymethyl group, said acyl group being an aliphatic, aromatic or aralkyl monocarboxylic acyl group of from 2 to 22 carbon atoms.

8. 2 (3 nitro 1,3 dimethylbutyl)-4,4,dirnethyl-2- oxazoline.

9. The nit-ro-oxazoline compounds represented by the following structural formula:

wherein R is the phenyl radical and R and R are selected from the group consisting of hydrogen, alkyl radicals having from 1 to 3 carbon atoms, hydroxymethyl radicals, and acyloxymethyl group, said acyl group being an aliphatic, aromatic or aralkyl monocarboxylic acyl group of from 2 to 22 carbon atoms.

Cal

10. The nitro-imidazoline compounds represented by the following structural formula:

1 (ll-R2 N wherein Y is selected from the group consisting of lower alkyl, aryl, arylalkyl, and hydroxyalkyl radicals of from 1 to 7 carbon atoms; R is selected from the group consisting of hydrogen and alkyl, arylalkyl, alkenyl, and aryl radicals having from 1 to 20 carbon atoms; and R and R are selected from the group consisting of hydrogen and alkyl radicals having from 1 to 3 carbon atoms.

11. The nitro-imidazoline compounds represented by the following structural formula:

wherein Y is selected from the group consisting of lower alkyl, aryl, arylalkyl and hydroxyalkyl radicals of from 1 to 7 carbon atoms; and R and R are selected from the group consisting of hydrogen and alkyl radicals having from 1 to 3 carbon atoms.

12. The nitro-imidazoline compounds represented by the following structural formula:

wherein R is arylalkyl radical corresponding to the formula where x is an integer of from 1 to 14; Y is selected from the group consisting of alkyl, aryl, arylalkyl, and hydroxyalkyl radicals of from 1 to 7 carbon atoms; and R and R are selected from the group consisting of hydrogen and alkyl radicals having from 1 to 3 carbon atoms.

13 15. The nitro-imidazoline compounds represented by the following structural formula:

l s HzC-(|J-R2 Y-N N H|CCHzC-CH;, R1 N02 wherein R is an alkenyl radical having from 2 to 20 carbon atoms; Y is selected from the group consisting of alkyl, aryl, arylalkyl, and hydroxyalkyl radicals of from 1 to 7 carbon atoms; and R and R are selected from the group consisting of hydrogen and alkyl radicals having from 1 to 3 carbon atoms.

16. The nitro-imidazoline compounds represented by the following structural formula:

HzO-UR2 Y-N N t E HC|JOH2CCH3 Rt N Ca wherein R is the phenyl radical; Y is selected from the group consisting lower alkyl, aryl, arylalkyl, and hydroxyalkyl radicals; and R and R are selected from the group consisting of hydrogen and alkyl radicals having from 1 to 3 carbon atoms.

17. A process for the production of a nitro azoline comprising the steps of:

(a) preparing a mixture, at a mole ratio of about 1:1, of a secondary nitroalkane with an ethenyl azoline represented by the following formula:

wherein X is selected from the group O and consisting of R and R are selected from hydrogen and alkyl radicals of from 1 to 3 carbon atoms,

(b) heating said mixture at reflux temperature in the presence of from about 0.5% to about 5% 'by weight, based on the weight of said ethenyl azoline of an acid condensation catalyst until the temperature has risen to about 150 C., and the said nitroazoline compound has been produced, and

(c) recovering the said nitro azoline.

18. The process of claim 17 wherein the Z-ethenyl azoline is a 2-ethenyl-2-oxazoline.

19. The process of claim 17 wherein the Z-ethenyl azoline is a 2-ethenyl-2-imidazoline.

20. A process for the production of a nitroazoline comprising the steps of (a) preparing a mixture of a 1-hydroxy-2-alkyl-2- nitroalkane and a 2-substituted-2-azoline at a mole ratio of about 1:1 in the presence of an inert solvent and from about 0.5% to about 5% by weight, based on the Weight of said 2-substituted-2-azoline, of an acidic condensation catalyst,

(b) heating said mixture at a temperature of from about C. to about 200 0, simultaneously removing therefrom the water of reaction released by said heating, until the reaction is substantially complete, and

(c) recovering the said nitro azoline from the reaction mixture.

21. The process of claim 20 wherein the 2-substituted- 2-azoline is a 2-substituted-2-oxazoline.

22. The process of claim 20 wherein the 2-substituted- 2-azoline is a Z-substituted-Z-imidazoline,

23. A process for the production of a nitro-azoline comprising the steps of:

(a) preparing a mixture of 2-substituted-2-azoline with a formaldehyde source and a secondary nitroalkane at a mole ratio of about 1:1:1 and about 0.5 to about 5% by weight, based on the weight of said oxazoline, of a condensation catalyst and,

(b) heating said mixture at a temperature of from about 100 C. to about 200 C., simultaneously removing therefrom the water of reaction released by said heating, until the reaction is substantially complete and (c) recovering the said nitroazoline from the reaction mixture.

Elderfield, Heterocyclic Compounds, vol. 5, p. 519.

Kozlov et al.: Chem. Abstracts, vol. 51 (1957), columns 11267-8.

ALEX MAZEL, Primary Examiner.

R. GALLAGHER, Assistqnt gxqminer,

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,354,171 November 21, 1967 Herbert L. Wehrmeister It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Columns 7 and 8, TABLE 1, fourth column, line 6 thereof, for "l-amino2methyll,3-propanediol" read Z-amino-Z- methyll,3propanediol column. 10, lines 69 to 75, column 11, lines 38 to 44., and column 12, lines 38 to 44, for that portion of each formula reading CH 3 -CCH read (II-CH column 13, lines 19 to 26, for that portion of the formula I reading "NC read N0 line 28, before "lower" insert Signed and sealed this 24th day of December 1968.

(SEAL) Attest:

EDWARD J. BRENNER Commissioner of Patents EDWARD M.FLETCHER,JR. Attesting Officer 

1. THE NITRO-AZOLINE COMPOUNDS REPRESENTED BY THE FOLLOWING STRUCTURAL FORMULA:
 17. A PROCESS FOR THE PRODUCTION OF A NITRO AZOLINE COMPRISING THE STEPS OF: (A) PREPARING A MIXTURE, AT A MOLE RATIO OF ABOUT 1:1, OF A SECONDARY NITROALKANE WITH AN ETHENYL AZOLINE REPRESENTED BY THE FOLLOWING FORMULA: 